Coloration of textile and other materials



Patented June 4, 194i) i UNITED STATES PATENT OFFICE" COLOBATION or TEXTILE AND OTHER MATERIALS George Holland Ellis and Henry CharlesOlpin, Spondon, near Derby, England, assignors to Celanese Corporation oi America, a corporation of Delaware Y No Drawing. Application October 2, 1937, SeiiigsNo. 166,970. In Great Britain October 12,

22 Claims. (Cl. 260-457) This invention relates'to improvements in the hydroxyethyl) amino-diphenyl havi the struccoloration of textile and other materials, and tural formula particularly of materials containing organic esters and ethers of cellulose. H-Om0m-nnO-O It has been discovered that substances which a 5 are sulphate esters of aromatic compounds NO:

(other than azo compounds and amino substiand of 1 1 -3 (p-hydroxyethyl) amtuted anthmquinones) containing a hydroxy" ino-4-nitrobenzene having the structural foralkyl group, a nuclear nitro group and an auxomula l0 chrome group have very valuable dyeing propo erties, particularly for textile and other mate- NH rials containing organic esters and ethers of.

cellulose, and the present invention includes the manufacture of these dyestuffs, the dyestufl's themselves, processes for the coloration of materials with the. dyestufis and the colored m'a- PIE-030111011 terials obtained.

The dyestuffs may be sulphato esters of relatively simple compounds containing only a single or in difi rent nuclei, g" as in the sulphato 2o aryl nuclgllsi fi' esters of 2,4-dinitro-4'-(p-hydroxyethyl) aminoethyl) amino-benzene having the structural'fordiphenylamlne having the structural. f ula mula . N0: NH-CHaCHzOH N0,- n NH- H HOH N0 N O C :C I v '25 and in the sulphato esters of other N-substitution derivatives of 2,4-dinitro-4'-amino-diphencl ylamine wherein one or both hydrogen atoms of the 4'-amino group is substituted by a hydroxy- 30 alkyl group. When only one hydrogen atom of zA-dinitro-l-fp -hydroxyethyl) amino-benzene an amino group is replaced by a sulphato-alkyl having the structural formula group the other hydrogen atom may or may not be replaced by another organic radicle, e. g., an

' alkyl group. as, for instance, a methyl or ethyl group. In all these compounds the auxochrome group necessary to the dyestuffs of the present invention is the amino group. However, other auxochrome groups may be present, e. g., phe- 40 nolic groups. 4

0t especial importance according to the present invention are dyestuffs in-which the nitro group is the sole chromophore group.

and other nitro-hydroxyalkylamino-benzenes, The sulphato-allwl groups present in the dye- -toluenes and naphthalenes. Of particular imstuffs of the present invention may be directly 45 portance, however, are dyestuffs which contain linked to an aryl residue or may be linked to an two or more aryl nuclei linked together directly, aryl residue through nitrogen, as in the case of as in diphenyl and similar diaryl compounds, or the sulphato esters of hydroxyalkylamino comindirectly, e. g., through an oxygen atom, a sulpounds mentioned above, through oxygen,. as in I phur atom or a -NH-, CHz-, -CO-, the case of thesulphato esters of hydroxyalkyl 5c -CO--NH-, or other group. Special mention ethers. or through sulphur, as in the case of the may be made of compounds containing more sulphato esters of hydroxyalkyl thioethers. Exthan one aryl nucleus and containing nitro and amples of such compounds are the sulphato eshydroxyalkyl groups either in the same nucleus, ters of nitro anthraquinone derivatives which e. g., as in the sulphato esters of 3-nitro-4-(pcontain a hydroxyalkyl group linked to the aryl 55 nucleus through oxygen or sulphur and an auxochrome group other than an amino group.

The dyestuffs may contain a single sulphatoalkyl group or may contain two or more sulphatoalkyl'groups attached to the same aryl nucleus or to different aryl nuclei. Again, two sulphatealkyl radicles may be linked to an aryl nucleus through the same nitrogen or other atom as, for example, in the case of the di-sulphato esters of di-(hydroxyalkyl) amino-aryl compounds. Furthermore, the dyestuffs may contain two or more sulphato ester groups attached to the same alkyl radicle, as in the case of the disulphato esters of aryl compounds containing il-y-dioxy-propyl amino radicles.

The dyestufis may contain, in addition to the above mentioned radicles, other suitable constituents, e. g., halogen atoms and alkyl, alkoxyl, amino and acidylamino groups.

The dyestuffs of the present invention may be produced by various processes. Thus an aromatic compound containing a nuclear nitro group, an auxochrome group and a hydroxyalkyl group may be converted into the corresponding sulphuric acid ester by sulphation, e. g., by treatment with concentrated sulphuric acid. Again, a sulphate-alkyl group may be introduced into a nitro-aromatic compound containing an amino group, or both a hydroxy or mercapto group and another auxochrome group, e. g., an amino group, by means of a sulphato-alkylating agent, e. g., a halogen alkyl sulphate such as B-chlorethyl-sulphate.

Dyestuifs containing more than one aryl group may be synthesised by reacting an aryl compound containing a halogen atom with an aryl compound containing an amino group containing an available hydrogen atom so as to elimaryl compounds containing a sulphato-alkyl group. Thus, for example, 2,4-dinitro-chlorbenzene may be reacted with 1-amino-4'N.ethylsulphato-ethyl-amino-benzene in the presence of alkali so as to form 2,4-dinitro-4N.ethyl-sulphato-ethyl-amino-diphenylamine ozmsoln or 2,4-dinitro-benzoyl chloride may be reacted with 1-amino-4N.ethyl-sulphato ethyl aminobenzene in the presence of alkali so as to form 4- 2',4dinitrobenZ0y1-amino) -N.ethyl sulphateethyl-anilinc having the structural formula The compound 1-amino-4N.ethyl-sulphato-ethylamino benzene may be prepared, for example, by

diazotising sulphanilic acid, coupling it with ethyl-p-hydroxyethyl aniline, reducing the azo compound so as to regenerate the sulphanilic acid and separating off the 1-amin0-4-N.ethylp-hydroxyethyl-amino-benzene CzHrOH so produced. By treating this derivative with strong sulphuric acid the corresponding sulphato CzHs ester is obtained. This method of production may be varied by effecting the sulphation of the ethyl-p-hydroxyethyl aniline before coupling it with the diazotised sulphanilic acid; the final sulphation step is then unnecessary. The introduction of hydroxyalkyl groups into aryl compounds in order to form compounds from which the dyestuffs of the present invention may be produced by sulphation may be effected by reacting the aryl compounds with ethylene chlorhydrin, glycerine chlorhydrin and similar compounds.

The dyestufis may be applied to the materials by any suitable method, for example, by immersing the materials in a bath containing the dyestuffs and Glauber's salt or by mechanical impregnation, printing or stencilling. In printing, the dyestuff may be mixed with a thickening agent, for example gum arabic, dextrin or the like, and the paste may be applied, for example, by printing with engraved rollers or through stencils, and the prints may afterwards be dried, steamed, aged and finished. v

The dyestuffs may be employed in conjunction with other dyestuiis or coloring matters and any other substances, according to the particular products required, and they may be employed in the coloration of materials made of or containing cellulose acetate, propionate, butyrate and other esters and mixed esters of cellulose, in the coloration of eifect threads obtained by the partial acetylation of cotton or regenerated cellulose or by treating alkalised cotton with a toluene sulpho chloride, or in the coloration of cellulose ethers,

The manufacture of 2,4 dinitro 4 ethyl sulphateethyl amino diphenylamine having the structural formula NO: CzHs Nor NH N\ 10 parts of 2,4-dinitro -4-(N-ethyl-fl-hydroxyethyl-amino)-diphenylamine prepared, for example, as described in Example 3 are dissolved in 100 parts of sulphuric acid of 96% concentration, the temperature being kept below 30 C. The solution is stirred for two hours and then poured into an excess of water, the dyestufi then being precipitated.

EXAMPLE 2 The manufacture of 2,4 dinitro 4' sulphato ethory diphenylamine having the structural formula NOONH-OOCims ole 10 parts of 2,4-dinitro-4'-p-hydroxy-ethoxydiphenylamine are introduced into 100 parts of sulphuric acid of 96% concentration, the temperature being maintained below 30 C. The so- Exam? 3 The manufacture of 2,4 dinitro 4' ethyl-p-hu drory ethyl-amino diphenylamine having the structural formula v Sulphanilic acid is diazotised and coupled with ethyl-p-hydroxyethyl-aniline in the ordinary way. The resulting azo dyestufi is reduced in aqueous solution and a mixture of 4-aminoethyl-s-hyclroxyethyl-aniline and regenerated thus obtained. To the solution sulphanilic' acid is added 2,4 dinitro-chlorbenzene in a sufilcient quantity to condense with both the sulphanilic acid and the 4-amino-N.ethyl-p-hydroxyethylaniline. The condensation proceeds rapidly at C. The 2,4-dinitro-4'-ethyl-p-hydroxyethylamino-diphenylamine is precipitated out and collected, the sulphanilic' acid condensation product remaining in solution as the sodium salt. The dyestuff obtained is then recrystallised from solution in a mixture of pyridine and methylated spirit.

EXAMPLE 4 The dyeing of cellulose acetate materials 3 parts of 2,4-dinitro-4'-sulphato-ethoxy-diphenylamine are dissolved in 3000 parts of water and the solution warmed to 45 C. 100 parts of cellulose acetate fabric or yarn are then worked in the bath for /4 hour. 20 parts of Glaubers salt are now added and the temperature raised to 80 C. when a further 20 parts oi Glaubers salt are added.- Dyeing is continued at this temperature for qnehour,at the end of which time the goods are rinsed and dried. A full golden yellow shade is obtained.

Having described our invention what we desire to secure by Letters Patent is: I

l. Dyestufls in which the sole chromophore groups are nitro groups and which are aryl compounds which contain at least one nuclear nitro group, at least one nuclear amino group and a sulphato group attached to a lower alkyl group which is linked to the aromatic residue by a linkage selected from the group consisting of direct linkage, linkage through an oxygen atom, linkage through a sulphur atom and linkage through an --NR,- group, where R is a substituent selected from the group consisting of hydrogen and an alkyl group.

2. Dyestuffs in which the sole chromophore groups are nitro groups and which are aryl compounds which contain at least one nuclear nitro group and a sulphate-alkyl group selected from the group consisting of sulphato-methyl, sulphato-ethyl and sulphato-propyl which is linked to the aromatic residue through an 41%- group, where R is a substituent selected from the group consisting of hydrogen and an alkyl group.'

3. Dyestuffs in which the sole chromophore groups are nitro groups and which are aryl compounds which contain at least two aryl nuclei linked together by a linkage selected from the group consisting of direct linkage, linkage through an oxygen atom, through a sulphur atom, through an 'NH- group, through a CH:-- group, through a CO group and through a -CONH- group, and which contain a sulgroup, through 9.

oxygen atom,

, groups are nitro groups and which phato-alkyl group selected sisting of sulphato-methyl, sulphato-ethyl and sulphato-propyi, a nuclear nitro group and-an auxochrome .group.

'4. Dyestuffs in which the sole chromophore groups are nitro groups and which are aryl compounds which contain'at least two aryl nuclei linked together by a linkage selected from the group consisting of direct linkage, linkage through an oxygen atom, through a sulphur atom, through an --NH- group, through a --CHa-- -CO group and through a -CO-NH group, and which contain a nitro group as a substituent in an aryl nucleus and a sulphate-alkyl group selected from the groupconsisting of sulphato-methyl, sulphato-ethyl and sulphato-propyl linked to an aryl nucleus through an -NR- group, where R. is a substituent selected from the group consisting of hydrogen and an alkyl group.

5. Dyestuffs in which the sole chromophore groups are nitro groups and which are diphenylamines which contain a nitro group as a substituent in one of the phenyl nuclei, an amino group as a substituent in one of the phenyl nuclei and a sulphato-alkyl group selected from the group consisting of sulphato-methyl, sulphato-ethyl and sulphato-propyl-linked to one of the phenyl nuclei by a linkage selected from the group consisting of direct linkage, linkage through an through a sulphur atom and through an -NRr-' group, where R is a substituent selected from the group consisting of hydrogen and an alkyl group.

6. Dyestuffs in which the sole chromophore groups are nitro groups and which are diphenyl amines which contain 3. nitro group as a substituent in one of the phenyl nuclei and a sulphato-alkyl group selected from the group consisting of sulphato-methyl, sulphato-ethyl and sulphato-propyl linked to one of the phenyl nuclei through an -NR gr up, where R. is a substituent selected from the g oup consisting of hydrogen and an alkyl group.

"I. Dyestuffs in phato-propyl linked to the other of the phenyl nuclei through an -NR group, where R. is a substituent selected from the group consisting of hydrogen and an alkyl group.

8. Dyestufi's in which the sole chromophore are diphenylamines which contain 9. nitro group as a substituent in one of the phenyl nuclei and a sulphato-alkyl group selected from the group consisting of sulphato-rnethyl, sulphato-ethyland which the sole chromophore groups are nitro groups and which are diphenyl from the group con- 7 the group consisting V of sulphato-methyl, sulphate-ethyl and sulsulphato-propyl linked to the other of the phenyl v nuclei through an oxygen atom.

9. The dyestufi 2,4-dinitro-4'-N.ethyl-sulphato-ethyl-amino-diphenylamine.

10. The dyestufl 2,4 -dinitro- 4 -sulphatoethoxy-diphenylamine.

11. Process for the manufacture of dyestuffs, which comprises treating with a sulphating agent aryl compounds which contain nuclear nitro groups as sole chromophore groups and which contain at least one auxochrome group and at least one hydroxyaikyl group.

12; Process for the manufacture of dyestuffs, which comprises treating with sulphuric acid aryl compounds which contain nuclear nitro groups as sole chromophore groups and which contain at least one auxochrome group and at least one hydroxyalkyl group in which the alkyl radicle is a lower alkyl radicle.

13. Process for the manufacture of dyestuffs, which comprises subjecting to treatment with sulphuric acid aryl compounds which contain nu clear nitro groups as sole chromophore groups, at least one nuclear amino group and a hydroxyalkyl group selected from the group consisting of hydroxymethyl, hydroxyethyl and hydroxypropyl groups which is linked to the aryl residue by a linkage selected from the group consisting of direct linkage, linkage through an oxygen atom linkage through a sulphur atom and linkage through an -NR- group, where R is a substituent selected from the group consisting of hydrogen and an alkyl group.

14. Process for the manufacture of dyestuffs, which comprises subjecting to treatment with sulphuric acid aryl compounds which contain nuclear nitro groups as sole chromophore groups and which contain a hydroxyalkyl group selected from the group consisting of hydroxymethyl, hydroxyethyl and hydroxypropyl groups linked to the aryl residue through an NR- group, where R is a substituent selected from the group consisting of hydrogen and an alkyl group.

15. Process for the manufacture of dyestuffs, which comprises subjecting to treatment with sulphuric acid aryl compounds which contain nuclear nitro groups as sole chromophore groups, at least one hydroxyalkyl group selected from the group consisting of hydroxymethyl, hydroxyethyl and hydroxypropyl groups and an auxochrome group, and which contain at least two aryl nuclei linked together by a linkage selected I from the group consisting of direct linkage, linkage through an oxygen atom, through a sulphur atom, through an NH group, through a CH2 group, through a -CO- group and through a -CONH- group.

16. Process for the manufacture of dyestuffs, which comprises subjecting to treatment with sulphuric acid aryl compounds which contain nuclear nitro groups as sole chromophore groups, which contain at least two aryl nuclei linked together by a linkage. selected from the group consisting of direct linkage, linkage through an oxygen atom, through a sulphur atom, through an NH group, through a -CH2 group, through a CO group and through a CO-NH group, and which contain a hydroxy-alkyl group selected from the group consisting of hydroxymethyl, hydroxyethyl and hydroxypropyl groups linked to an aryl nucleus through an NR- group, where R is a substituent selected from the group consisting of hydrogen and an alkyl group.

17. Process for the manufacture of dyestuffs, which comprises subjecting to treatment with sulphuric acid aryl compounds which contain nuclear nitro groups as sole chromophore groups and which are diphenylamines which contain a nitro group as a substituent in one of the phenyl nuclei, an amino group as a substituent in one of the phenyl nuclei and a hydroxy-alkyl group selected from the group consisting of hydroxymethyl, hydroxyethyl and hydroxypropyl groups linked to one of the phenyl nuclei by a linkage selected from the group consisting of direct linkage, linkage through an oxygen atom, linkage through a sulphur atom and linkage through an NR-- group, Where R is a substituent selected from the group consisting of hydrogen and an alkyl group.

18. Process for the manufacture of dyestuffs, which comprises subjecting to treatment with sulphuric acid aryl compounds which contain nuclear nitro groups as sole chromophore groups and which are diphenylamines which contain 8. nitro group as a substituent in one of the phenyl nuclei and a hydroxy-alkyl group selected from the group consisting of hydroxymethyl, hydroxyethyl and hydroxypropyl groups linked to one of the phenyl nuclei through an NR group, where R is a substituent selected from the group consisting of hydrogen and an alkyl group.

19. Process for the manufacture of dyestufls, which comprises subjecting to treatment with sulphuric acid aryl compounds which contain nuclear nitro groups as sole chromophore groups and which are diphenylamines which contain a nitro group as a substituent in one of the phenyl nuclei and a hydroxyalkyl group selected from the group consisting of hydroxymethyl, hydroxyethyl and hydroxypropyl groups linked to the other of the phenyl nuclei through an -NR- group, where R is a substituent selected from the group consisting of hydrogen and an alkyl group.

10. Process for the manufacture of dyestuffs, which comprises subjecting to treatment with sulphuric acid aryl compounds which contain nuclear nitro groups as sole chromophore groups and which are diphenylamines which contain a nitro group as a substituent in one of the phenyl nuclei and a hydroxyalkyl group selected from the group consisting of hydroxymethyl, hydroxyethyl and hydroxypropyl groups linked to the other of the phenyl nuclei through an oxygen atom.

21. Process for the manufacture of dyestuffs, which comprises subjecting to treatment with sulphuric acid the compound 2,4-dinitro-4-(N- ethyl-N-p-hydroxyethyl-amino) -diphenylamine.

22. Process for the manufacture of dyestufis, which comprises subjecting to treatment with sulphuric acid the compound 2,4-dinitro-4-hydroxy-ethoxy-diphenylamine.

GEORGE HOLLAND ELLIS. HENRY CHARLES OLPIN. 

